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theAngryLittleBunny
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WARNING: Explosive reaction between pool chlorine chemicals
Maybe most people here know about it, but I'll still post it for anyone who might not. Since I've been doing chemistry for 6 years now and this
accident happened to me just recently, maybe 1 or 2 months ago.
I generated chlorine gas by adding HCl in a flask with TCCA and after generating a bit of chlorine I thought I should make an excess to displace the
air. However, I didn't feel like crushing up more TCCA tablets, so I just added 10g of calcium hypochlorite into the flask and continued. Maybe one or
two minutes later the flask just exploded while I sat in front of it. I had tiny glass shards on my glasses and my face. I was super lucky and only
ended up with a few scratches in my face and my hand. I had no clue what happened, but after researching a bit, turns out TCCA reacts with hypchlorite
to nitrogen trichloride and a carbonate salt (C3N3O3Cl3 + 3Ca(OCl)2 -> 3CaCO3 + 3NCl3). I don't know if that's something people who do chemistry
generally know about so I wanted to post it so no one else makes the same mistake. I think I just underestimated the danger of these chemicals just
because they are OTC.
In general, don't mix TCCA (or Na-DCCA) with any kind of base, including NaOH or Na2CO3. Someone told me they had TCCA powder that was contaminated
with Na2CO3 explode. In solution it doesn't result in any explosion (in my experience, still don't try it), when dissolving TCCA or Na-DCCA in a NaOH
solution you will see that it starts fizzing a bit giving off an colourless and odourless gas, I'm sure that is nitrogen from tiny amounts of NCl3
decomposing very quickly after being generated. I tried making NaOCl that way (which is not too easy to get here cheaply) which doesn't work. As long
as you keep TCCA/ Na-DCCA in neutral or acidic conditions it seems to be safe.
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fredsci93
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That's terrifying, I can't believe I had never heard about that, makes some sense in retrospect though since CA is a urea derivative.
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theAngryLittleBunny
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Quote: Originally posted by fredsci93  | | That's terrifying, I can't believe I had never heard about that, makes some sense in retrospect though since CA is a urea derivative.
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I never heard of it either, there were a few accidents from people who used it for their pools because they mixed two different pool chlorinating
chemicals (one with TCCA/ Na-DCCA, one with Ca(OCl)2). This can easily happen since Na-DCCA and Ca(OCl)2 are both used to quickly raise hypochlorite
levels in pools (so called shock chlorination) since they are both water soluble. Usually the containers for these from the same brand look pretty
much identical. In one case a couple mixed them in the kitchen which resulted in 5 violent explosions destroying the entire kitchen, luckly they
weren't in the kitchen when it happened and survived.
Afterwards I looked on the label and there is said to not mix them or it could cause an explosive reaction, maybe I should have read that earlier lol.
If you mix TCCA/ Na-DCCA with Ca(OCl)2 it's not just an explosion risk, it WILL explode.
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MadHatter
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Witch's Mix
C3Cl3N3O3 + 3Ca(OCl)2 ---> 3CaCO3 + 3NCl3
Nitrogen trichloride theoretical stoichiometric yield: 54.6%
It can be detonated by light, heat, shock and contact with organics.
From opening of NCIS New Orleans - It goes a BOOM ! BOOM ! BOOM ! MUHAHAHAHAHAHAHA !
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Monoamine
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Thank you for the warning and self experiment. So I guess the "safe" way to make Cl2 is just to use sodium hypochlorite and HCl.
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karlos³
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The worst is that NCl3 even explodes in aqueous medium, something which NI3 is not able to.
Yeah I knew about that, it is pretty unknown though.
There is some aldehyde amidation method which uses that which we ruled out as far too dangerous.
What a relief you still have all your fingers and both eyes!
[Edited on 7-12-2021 by karlos³]
verrückt und wissenschaftlich
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woelen
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I started a thread about this 13 years ago: https://www.sciencemadness.org/whisper/viewthread.php?tid=11...
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MadHatter
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Too Dangerous/Unstable
NCl3, NI3, sulphur or phosphorus with chlorates and ALL
hypergolic mixtures. I don't even want to be near them.
From opening of NCIS New Orleans - It goes a BOOM ! BOOM ! BOOM ! MUHAHAHAHAHAHAHA !
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pantone159
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Would cyanuric acid (instead of the chlorinated TCCA or Na-DCCA) cause the dangerous situation as well?
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MadHatter
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Cyanuric Acid
C3H3N3O3 + 3Ca(OCl)2 ---> 3CaCO3 + 2NCl3 + NH3
Nitrogen trichloride theoretical stoichiometric yield: 43.1%
If I have the equation correctly.
From opening of NCIS New Orleans - It goes a BOOM ! BOOM ! BOOM ! MUHAHAHAHAHAHAHA !
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woelen
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Yes, it does, I tried at test tube scale by mixing solid cyanuric acid, solid Ca(ClO)2 and adding a few
drops of water.
Madhatter's equation gives a hint in this direction. The reality is more complicated though. No free NH3, but also NH2Cl (smell!) and N2 (lot of
colorless gas is produced).
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teodor
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NCl3 should be an interesting compound. Alas, it has explosive properties. I am wondering, is it possible to stabilize NCl3 binding to some type of
complex salt and then study it as an anion?
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Bedlasky
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Teodor: I don't thing that it forms complex anions. I guess maybe some adduct, but I never read about it.
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teodor
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Bedlasky, I really wanted to write "complex or adduct" but I forget the second word, thank you. Yes, I know PCl3 very often forms such adducts.
Update.
Also, quite interesting, from "Comprehensive Inorganic Chemistry":
".. the endothermic character and resulting instability on NCl3 and NI3 ... results not from ... weakness of the N-Cl or N-I bond but rather from ...
the stability of the multiple bond in the N2 molecule. The energy of formation of N2 molecules from free N atoms is so large that nitrogen compounds
unless they contain bonds of rather high energy, tend to have negative heats of formation..."
[Edited on 8-12-2021 by teodor]
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woelen
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NCl3 is really nasty stuff. It explodes very easily, but its explosions also are very powerful. Even a single drop of liquid in the bottom of a test
tube will lead to shattering and flying pieces of glass if it explodes. Really dangerous stuff and if you value your fingers, hands and eyes, then I
would be very cautious with NCl3.
When I did the experiment with Na-DCCA and Ca(ClO)2 and saw the drop of NCl3 I was shit scared and quickly put the test tube aside and went away, just
waiting it out. Fortunately the drop of NCl3 did not explode and simply was consumed by all alkaline stuff around.
I worked with other explosive stuff (ClO2 and even ClN3), but these are less scary, because they are gaseous and explosions of that tend to be much
less powerful (lower density, much larger starting volume). A test tube with exploding ClO2 does not shatter, but the same weight of material (e.g.
NCl3) concentrated in a small drop in the bottom of a test tube does lead to flying glass splinters.
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teodor
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Benzene solution of NCl3 is "somehow stable in the dark" as some sources do mention, but that means somebody who wants to experiment with tiny
quantities can also do it in a solution to lower the power of the possible explosion.
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Admagistr
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I think that NCl3 could also be made by electrolysis of a concentrated solution of NH4Cl. Has anyone tried it, does anyone know anything about this?
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theAngryLittleBunny
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| Quote: Originally posted by karlos³ | The worst is that NCl3 even explodes in aqueous medium, something which NI3 is not able to.
Yeah I knew about that, it is pretty unknown though.
There is some aldehyde amidation method which uses that which we ruled out as far too dangerous.
What a relief you still have all your fingers and both eyes!
[Edited on 7-12-2021 by karlos³] |
Yeah that's because NCl3 seperates out as an oil that sinks so it can easily collect there. If you put ammonia in an excess of bleach you'll quickly
get a blob of yellow NCl3 forming at the bottom, this stuff is really scary.
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theAngryLittleBunny
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Absolutely, since hypochlorite would turn the cyanuric acid into TCCA. A lot of things that have nitrogen in the -3 oxidation state will do that, so
never mix that with hypochlorite. I think any compound that would form ammonia through alkaline hydrolysis would do that for sure, like urea or any
amide.
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theAngryLittleBunny
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| Quote: Originally posted by woelen | NCl3 is really nasty stuff. It explodes very easily, but its explosions also are very powerful. Even a single drop of liquid in the bottom of a test
tube will lead to shattering and flying pieces of glass if it explodes. Really dangerous stuff and if you value your fingers, hands and eyes, then I
would be very cautious with NCl3.
When I did the experiment with Na-DCCA and Ca(ClO)2 and saw the drop of NCl3 I was shit scared and quickly put the test tube aside and went away, just
waiting it out. Fortunately the drop of NCl3 did not explode and simply was consumed by all alkaline stuff around.
I worked with other explosive stuff (ClO2 and even ClN3), but these are less scary, because they are gaseous and explosions of that tend to be much
less powerful (lower density, much larger starting volume). A test tube with exploding ClO2 does not shatter, but the same weight of material (e.g.
NCl3) concentrated in a small drop in the bottom of a test tube does lead to flying glass splinters. |
I poured 10g of Ca(OCl)2 on top of over 100g of TCCA, not sure how much NCl3 this could make in practice. It was a 1L flask, and it just bursted and
glass shards were lying everywhere within a 4m radius of where it happened. I was sitting right in front of it so I'm really surprised I got away
pretty much completely unharmed. And after the accident I think I came across a thread that talked about that. But it wasn't so easy to find so I
think another post about this might be useful.
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clearly_not_atara
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TCCA and its derivatives have caused other explosions as well; see e.g. the chlorination of benzaldehyde. Perhaps we should put a warning in the TCCA
article on the SM wiki, since it is a common chemical that even beginners often use while not being aware of the risks.
The partially dehalogenated TCCA can give off HCl and N2, while alkaline hydrolysis can generate chloramines. And hypochlorites are a concern.
[Edited on 04-20-1969 by clearly_not_atara]
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theAngryLittleBunny
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| Quote: Originally posted by clearly_not_atara | TCCA and its derivatives have caused other explosions as well; see e.g. the chlorination of benzaldehyde. Perhaps we should put a warning in the TCCA
article on the SM wiki, since it is a common chemical that even beginners often use while not being aware of the risks.
The partially dehalogenated TCCA can give off HCl and N2, while alkaline hydrolysis can generate chloramines. And hypochlorites are a concern.
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Oh shiiiit, when I started with chemistry I put solid TCCA to Benzaldehyde in an attempt to make benzoyl chloride. I had no clue this stuff was so
dangerous, I think a warning would be a good idea.
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Morgan
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As an aside, I used to mix prilled ammonium nitrate with calcium hypochlorite and it made some unknown violent snap, crackle, popping sound
spontaneously starting after a minute or so after the granules were combined one on top the other or you could just wet it. Never was it a seemingly
threatening reaction but the pool chlorine hypochlorite product was only 65% with inert ingredients of some sort if that was a factor.
Anyway it seems to liquify and froth somewhat as the reaction takes place if you put it in a wide can and although the popcorn effect was most
entertaining like dozens of mini firecrackers going off at the same time for a little less than a minute duration, it was kind of loud but not too. I
never knew just what the chemical reaction was. Also youtube has never featured it to my knowledge. I mixed about a pound one time.
I can't say it's safe to try but it never seemed to do more than what I described. I would just like to know what cusp of an explosive was formed and
destroyed before it ever became unified enough to become forceful. I avoided the fumes too in which distance from an uncertain reaction is always a
good idea. Some of those hypochlorite and brake fluid videos are pretty snap crackly but the prilled NH4NO3 is just a bit more energetic on that
spectrum. It never made a flame, just steamy smoke and machine gun pops.
Don't take chances with this reaction. I was younger and foolish when I did it. Maybe it's relatively safe, maybe not.
Maybe the heat of the reaction sets off tiny droplets before the formation of any real quantity of NCl3 can happen.
Wiki tidbits on nitrogen trichloride .. .
"Autoignition temperature 93 °C (199 °F; 366 K)"
"The compound is prepared by treatment of ammonium salts, such as ammonium nitrate with chlorine."
"The pure substance (rarely encountered) is a dangerous explosive, being sensitive to light, heat, even moderate shock, and organic compounds."
And for review ...
"Pierre Louis Dulong first prepared it in 1812, and lost two fingers and an eye in two explosions. In 1813, an NCl3 explosion blinded Sir Humphry Davy
temporarily, inducing him to hire Michael Faraday as a co-worker. They were both injured in another NCl3 explosion shortly thereafter."
[Edited on 9-12-2021 by Morgan]
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MadHatter
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Modified equation
woelen, you're probably right about the equation considering you
noticed chloramine. I should've realized this when thinking back
to what happens when ammonia and bleach are mixed together.
It probably depends on the temperature. Anyway:
2C3H3N3O3 + 6Ca(OCl)2 ---> 6CaCO3 + 3NCl3 + 3NH2Cl
Reworked equation I came up with. I detest unbalanced equations.
Nitrogen trichloride theoretical stoichiometric yield: 32.3%
Chloramine theoretical stoichiometric yield: 13.8%
For ammonia and bleach I remember:
NH3 + NaOCl ---> NaOH + NH2Cl (WARM)
2NH3 + NaOCl ---> NaCl + N2H4 + H2O (COLD)
Admagistr, electrolysis of NH4Cl is extremely dangerous because it
produces NH4ClO3 in addition to NCl3. I'm not sure which is more
unstable: Ammonium chlorate or nitrogen trichloride. IMHO, anybody
who does this gets my nomination for the Darwin Award.
[Edited on 2021/12/9 by MadHatter]
From opening of NCIS New Orleans - It goes a BOOM ! BOOM ! BOOM ! MUHAHAHAHAHAHAHA !
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woelen
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Actually, NH4ClO3 is not that dangerous in solution. But I doubt that this will be formed when you electrolyze NH4Cl. You get Cl2 at the anode, which
forms NCl3 with the amonium ions. At the cathode you get NH3 and H2. On mixing, the NH3 will react with NCl3 and also with Cl2, giving N2, NH2Cl and
maybe even some NH2NH2.
NH4ClO3 is another funny beast, but not in this context.
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